EP0179547B1 - Thin film solar cell with free tin on transparent conductor - Google Patents

Thin film solar cell with free tin on transparent conductor Download PDF

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Publication number
EP0179547B1
EP0179547B1 EP19850304609 EP85304609A EP0179547B1 EP 0179547 B1 EP0179547 B1 EP 0179547B1 EP 19850304609 EP19850304609 EP 19850304609 EP 85304609 A EP85304609 A EP 85304609A EP 0179547 B1 EP0179547 B1 EP 0179547B1
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Prior art keywords
layer
transparent
characterised
solar cell
glow discharge
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EP19850304609
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German (de)
French (fr)
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EP0179547A1 (en )
Inventor
Kevin K. Mackamul
Don L. Morel
David P. Tanner
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ARCO SOLAR, INC. TE CAMARILLO, CALIFORNIE, VER. ST
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Atlantic Richfield Co
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03921Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including only elements of Group IV of the Periodic System
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02Details
    • H01L31/0224Electrodes
    • H01L31/022466Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy

Description

    Background of the invention
  • This invention relates to thin film solar cells and more particularly to such solar cells having a layer of free metal between the transparent conductive layer and the semi-conductor layer.
  • The art of thin film solar cells is well-known and improvements are being made therein in an effort to make such devices commercially practical. For example, amorphous silicon p-i-n structures are disclosed in U.S. Patent 4,385,200 and 4,388,482 issued to Hamakawa on May 24,1983 and June 14,1983, respectively. Another Hamakawa et al patent No. 4,410,559 issued October 18, 1983, provides more detailed teachings concerning the glow discharge techniques for depositing amorphous silicon films with various doping materials. Each of these patents is hereby incorporated by reference for their teachings of cell structures and methods of manufacture.
  • While the amorphous silicon solar cells seem quite simple, the continued development has identified numerous limiting factors in such cells. The above-referenced patents discuss various ways of improving overall cell efficiency. As indicated in those patents, a somewhat typical solar cell comprises a transparent substrate such as glass supporting a transparent conductor layer on which is deposited the amorphous silicon active device on which is deposited a back face, usually metallic, conductor. Current is carried from the device by means of the front transparent conductor and the back metallic conductor. It has long been recognized that improvements in conductor resistivity, particularly the transparent conductor, can reduce device internal resistance and thereby improve efficiency. The ability to maintain peak current output near the maximum operating voltage is commonly referred to as the cell fill factor, CFF, with the higher rating being preferable. Internal resistances of the various conducting layers and interfaces therebetween must be reduced to improve the CFF.
  • US-A-4.387.387 discloses a solar cell wherein a light transparent, current permeable nitride layer is interposed between the semiconductor layer and the light transparent conductor layer. The presence of the nitride layer is said to improve the photoelectric conversion characteristic and photoelectric conversion efficiency of the cell.
  • According to the present invention there is provided a solar cell comprising a transparent front face electrode, a thin film photovoltaic structure, and a back face electrode on said photovolatile structure, characterised by a light transparent layer of a metal in an elemental form on said front face electrode, said photovoltaics structure being on said metal layer.
  • According to the invention there is also provided a method for manufacturing a solar cell wherein a substrate having a transparent conductive layer of primarily tin oxide is positioned in a glow discharge chamber and semiconductor layers are deposited on said transparent conductive layer, characterised in that before deposition of said semiconductor layers, said transparent conductive layer is treated with a glow discharge for a time sufficient to generate an essentially transparent layer of tin in an elemental form on the surface of said transparent conductive layer.
  • According to the invention there is also provided a method for manufacturing a solar cell wherein a substrate having a transparent conductive layer of primarily tin oxide is positioned in a glow discharge chamber and semiconductor layers are deposited on said transparent conductive layer, characterised in that after deposition of a first semiconductor layer, said substrate provided with said transparent conductive layer and said first semiconductor layer is treated with a glow discharge including hydrogen gas for a time sufficient to generate an essentially transparent layer of tin in an elemental form at the interface of said transparent conductive layer and said first semiconductor layer.
  • The present invention may be better understood by reading the following detailed description of the preferred embodiments with reference to the accompanying single figure which is a cross-sectional illustration of a thin film solar cell according to the present invention.
  • With reference now to the figure there is illustrated a basic solar cell structure according to the present invention. In this embodiment the solar cell is formed on a transparent insulating substrate 10. In the preferred embodiment, this substrate 10 is relatively inexpensive soda lime glass having a thickness of about one millimeter. A transparent conductor, TC, layer 12 is deposited on substrate 10 to form a front face contact for the finished device. Layer 12 is typically 400 to 500 nm (4000 to 5000 angstroms) thick and is formed primarily from tin oxide, but may be doped with materials such as indium or fluorine as is well known in the art.
  • A free metal layer 14 is formed or deposited upon TC layer 12. In the preferred embodiments, layer 14 is tin which is either directly deposited by, for example, sputtering or is formed by reduction of a portion of the TC layer 12 in a glow discharge apparatus. Layer 14 has a thickness of about 1 to 5 nm (ten to fifty angstroms) and is greatly exaggerated in the drawing for purposes of illustration only. It is apparent that layer 14 must be sufficiently thin so as not to significantly interfere with transmission of light received through substrate 10.
  • As used herein, the terms free metal or free tin refer to the elemental form of the metal or tin free of any oxygen bonds. It does not necessarily mean that in the finished solar cell device a continuous layer of metal or tin exists in which the metal or tin atoms are bound extensively to each other. Instead it is likely that the free metal is actually incorporated into the structure of the first portion of the silicon layer 16 described below.
  • A photovoltaic semiconductor structure 16 is formed on conductor layer 14. In the preferred embodiment, structure 16 is a P-I-N amorphous silicon photovoltaic cell such as those taught in the above-referenced Hamakawa et al patents and would have a thickness of from about 500 to 700 nm (5000 to 7000 angstroms) overall. The individual P, I and N layers are not separately illustrated in the Figure in order to simplify the drawing.
  • The solar cell is completed by providing a back electrical contact 18 on the semiconductor structure 16. In the preferred embodiment, layer 18 is formed from aluminum and is deposited to a thickness of about 200 nm (2000 angstroms). Layer 18 may of course be formed from other conductive materials including transparent conductors such as are typically used for layer 12.
  • As noted above, reduction in internal device resistance in order to improve CFF has been a goal of much thin film solar cell research and development. The use of the free metal layer 14 according to the present invention has been found to significantly improve CFF. We believe this improvement is due to a reduction in resistance at the interface between the TC layer 12 and the semiconductor structure 16. The free metal which is preferably tin, when layer 12 is formed primarily from tin oxide, appears to make a good electrical contact to layer 12. Upon glow discharge deposition of the semiconductor 16 the free metal 14 is believed to alloy with the first portion of deposited semiconductor thereby forming a good electrical contact to the semiconductor 16. The net effect is believed to be a low resistance contact between layers 12 and 16 which results in the net improvement in cell performance in terms of CFF.
  • The preferred method of forming free metal layer 14 is performed in the same glow discharge apparatus which is used to deposit semiconductor layer 16. For example glow discharge apparatus such as that taught in the above-referenced U.S. Patent 4,410,559 would be suitable for this purpose. We have found that a free metal layer 14 may be formed on a TC layer 12 by exposing the TC layer to such a glow discharge in which a flow of hydrogen gas is provided. For example, about 3 nm (30 angstroms) of free tin may be formed on a tin oxide TC layer 12 by glow discharge treatment under the following conditions; hydrogen flowing at 100 standard cubic centimeters per minute, pressure of 200 Pa (1.5 torr), 30 watts of 13.56 MHz applied to 215 square inches of surface for six seconds.
  • The above process was discovered when hydrogen glow discharge was used with the intent of cleaning TC coated substrates prior to deposition of silicon. When unexpected improvements in CFF resulted from such cleaning steps, we realized that free metal was being generated and was responsible for the improved performance. In order to prove the presence of free metal as a result of the hydrogen glow discharge, sample devices were produced with free tin directly deposited upon a TC layer 12. For example, a TC coated substrate was placed in a sputtering chamber and a tin target was used to deposit a free tin layer having a thickness of about 3 nm (30 angstroms). This substrate was then moved to a glow discharge chamber wherein an amorphous silicon p-i-n structure was deposited. The device was then completed by deposition of an aluminum back contact 18. Upon testing, it was found that the cell fill factor was improved by the presence of a free tin. For example, the CFF of cells having the sputtered tin layer were about 0.73. Cells which did not have tin applied, either by sputtering or hydrogen glow discharge, but which were otherwise identical had CFF's of about 0.64.
  • While the effect of the free tin on the TC layer 12 was illustrated by direct deposition of tin on a TC layer, it is believed that the glow discharge technique for production of the free metal layer is preferred. The glow discharge equipment is typically automated so that the multiple silicon layers are deposited in an essentially continuous fashion without removing the substrate from the chamber. The generation of free metal layer 14 can be done as a first step of the glow discharge process without requiring any physical movement of the substrate. In addition to the obvious labor savings of this process, the chance of substrate contamination during movement of the substrate from an evaporation chamber to the glow discharge chamber is eliminated.
  • Examples of results obtained by using such a process are given in Table 1. The hydrogen glow conditions were the same as those specified above except that the time was varied to determine the effect on cell parameters. While CFF was significantly improved at processing times from 0.1 to five minutes cell efficiency was reduced as processing time was increased beyond 0.1 minute. Thus it appears that free tin in excess of the initial effective amount merely reduces light transmission through TC layer 12.
    Figure imgb0001
  • As indicated by Table 1 it appears that a hydrogen glow processing time of about 0.1 minute is preferred. However, such a short processing time may be too difficult to control to achieve uniform and reproducible results in a production situation. We have developed other glow discharge processes which generate free tin from TC layer 12 at a somewhat slower rate and therefore should be more easily controlled. One method is to use the hydrogen glow discharge process described above after an initial portion of the silicon layer 16 is deposited. This can conveniently be done after deposition of the P doped portion of layer 16, which portion is about 10 nm (100 angstroms) thick. This silicon layer masks the TC layer 12 or otherwise slows the reduction process, but does not stop it completely. Results equivalent to the 0.1 minute processing time of Table 1 are achieved with a glow discharge time of five minute.
  • Another approach to the glow discharge process is to use a nonreactive gas. The structure of the TC layer 12 surface is such that bombardment by essentially any gas will selectively remove oxygen, thereby producing free tin. A glow discharge process like that described above, but in which argon was substituted for hydrogen, gave the same improved results if longer processing time was used. Thus exposure of a tin oxide TC layer 12 to an argon glow discharge for one minute produces cell improvements corresponding to the direct sputtering of 3 nm (30 angstroms) of free tin onto layer 12.
  • While the effect of the free metal was proven by deposition of pure tin on the TC layer, it is apparent that other metallic elements may be present in the free metal layer 14. Thus, TC layer 12 may contain indium and other materials. When the metal layer 14 is formed by glow discharge reduction, it can be expected that some free metallic components other than tin will also be generated.
  • While the present invention has been illustrated and described with reference to a particular structure and methods of manufacture thereof, it is apparent that various modifications and additions can be made thereto within the scope of the present invention as defined by the appended claims.

Claims (10)

1. A solar cell comprising a transparent front face electrode (12), a thin film photovoltaic structure (16), and a back face electrode (18) on said photovoltaic structure (16), characterised by a light transparent layer (14) of a metal in an elemental form on said front face electrode (12), said photovoltaic structure (16) being on said metal layer (14).
2. A solar cell as claimed in Claim 1, characterised in that said transparent front face electrode (12) is supported on a transparent insulating substrate (10) through which incident light may be received.
3. A solar cell as claimed in Claim 1 or 2, characterised in that said transparent front face electrode (12) comprises primarly tin oxide.
4. A solar cell as claimed in Claim 1, 2 or 3, characterised in that said layer (14) is substantially transparent to visible light.
5. A solar cell as claimed in any one of Claims 1 to 4, characterised in that said layer (14) has a thickness of from 1 to 10 nm.
6. A method for manufacturing a solar cell according to Claim 1 wherein a substrate (10) having a transparent conductive layer (12) of primarily tin oxide is positioned in a glow discharge chamber and semiconductor layers (16) are deposited on said transparent conductive layer (12), characterised in that before deposition of said semiconductor layers (16), said transparent conductive layer (12) is treated with a glow discharge for a time sufficient to generate an essentially transparent layer (14) of tin in an elemental form on the surface of said transparent conductive layer (12).
7. A method as claimed in Claim 6, characterised in that said glow discharge includes hydrogen gas.
8. A method as claimed in Claim 6, characterised in that said glow discharge includes only nonreactive gases.
9. A method as claimed in Claim 6, characterised in that said glow discharge includes primarily only argon gas.
10. A method for manufacturing a solar cell according to Claim 1 wherein a substrate (10) having a transparent conductive layer (12) of primarily tin oxide is positioned in a glow discharge chamber and semiconductor layers (16) are deposited on said transparent conductive layer (12), characterised in that after deposition of a first semiconductor layer (16), said substrate (10) provided with said transparent conductive layer (12) and said first semiconductor layer (16) is treated with a glow discharge including hydrogen gas for a time sufficient to generate an essentially transparent layer (14) of tin in an elemental form at the interface of said transparent conductive layer (12) and said first semiconductor layer (16).
EP19850304609 1984-10-22 1985-06-27 Thin film solar cell with free tin on transparent conductor Expired EP0179547B1 (en)

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US06663648 US4584427A (en) 1984-10-22 1984-10-22 Thin film solar cell with free tin on tin oxide transparent conductor

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DE4000664A1 (en) * 1990-01-11 1991-07-18 Siemens Ag Transparent electrode for amorphous silicon photodiodes - comprises multilayer of alternate high and low oxygen content oxide layers
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US8729385B2 (en) 2006-04-13 2014-05-20 Daniel Luch Collector grid and interconnect structures for photovoltaic arrays and modules
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US9236512B2 (en) 2006-04-13 2016-01-12 Daniel Luch Collector grid and interconnect structures for photovoltaic arrays and modules
US8664030B2 (en) 1999-03-30 2014-03-04 Daniel Luch Collector grid and interconnect structures for photovoltaic arrays and modules
US9006563B2 (en) 2006-04-13 2015-04-14 Solannex, Inc. Collector grid and interconnect structures for photovoltaic arrays and modules
US9865758B2 (en) 2006-04-13 2018-01-09 Daniel Luch Collector grid and interconnect structures for photovoltaic arrays and modules
US8822810B2 (en) 2006-04-13 2014-09-02 Daniel Luch Collector grid and interconnect structures for photovoltaic arrays and modules
US20080011350A1 (en) * 1999-03-30 2008-01-17 Daniel Luch Collector grid, electrode structures and interconnect structures for photovoltaic arrays and other optoelectric devices
US8884155B2 (en) 2006-04-13 2014-11-11 Daniel Luch Collector grid and interconnect structures for photovoltaic arrays and modules
US8222513B2 (en) 2006-04-13 2012-07-17 Daniel Luch Collector grid, electrode structures and interconnect structures for photovoltaic arrays and methods of manufacture
US7635810B2 (en) * 1999-03-30 2009-12-22 Daniel Luch Substrate and collector grid structures for integrated photovoltaic arrays and process of manufacture of such arrays
US7982127B2 (en) 2006-12-29 2011-07-19 Industrial Technology Research Institute Thin film solar cell module of see-through type
FR2919428B1 (en) * 2007-07-27 2010-01-01 Univ Nantes Electrode optoelectronic component, comprising at least one layer of a transparent oxide coated with a metal layer, and corresponding optoelectronic component.
US20090107538A1 (en) * 2007-10-29 2009-04-30 Daniel Luch Collector grid and interconnect structures for photovoltaic arrays and modules
US8316590B2 (en) 2009-03-20 2012-11-27 Northern States Metals Company Support system for solar panels
US8256169B2 (en) 2009-03-20 2012-09-04 Northern States Metals Company Support system for solar panels
US8839573B2 (en) 2011-02-11 2014-09-23 Northern States Metals Company Spring clip
US9303663B2 (en) 2013-04-11 2016-04-05 Northern States Metals Company Locking rail alignment system

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JPS61100979A (en) 1986-05-19 application
US4584427A (en) 1986-04-22 grant
DE3569438D1 (en) 1989-05-18 grant
EP0179547A1 (en) 1986-04-30 application
JPH0624249B2 (en) 1994-03-30 grant

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